14278-30-9Relevant academic research and scientific papers
Trizaine-based dehydrative condensation reagents bearing carbon-substituents
Kitamura, Masanori,Komine, Sayaka,Kunishima, Munetaka,Yamada, Kohei
, (2020/02/22)
Herein, we report on the synthesis of alkyl-, aryl-, and alkynyl-substituted chlorotriazines and their ammonium salts, and demonstrate their utility in dehydrative condensation reactions. Although the electrophilicity of these reagents is mainly dependent on the hybridization of the carbon-substituents, it was found that bulky 2,6-dimethylphenyl group-substituted reagents resulted in the highest product yields because of a slight increase in reagent electrophilicity and/or steric hindrance favorable for desired dehydrative condensation reactions.
Reactions of N-acylaziridines with sodium metal and sodium naphthalenide. Elimination of olefines
Lin, Pen-Yuan,Bellos, Konstantinos,Werry, Juergen,Assithianakis, Petros,Weiss, Rainer,Mall, Thomas,Bentz, Gunther,Stamm, Helmut
, p. 270 - 278 (2007/10/03)
Reactions of N-acylaziridines 1a-g (N-benzoyl except 1d) with sodium or naphthalenide N.- in THF provide a variety of products that usually arise via the aziridino ketyls 2. Homolytic ring opening of 2 generates the amidatoalkyl radicals 3. Only with a very short reaction time were small amounts of benzil or benzoylnaphthalenes obtained indicating a reversible trapping of 2 by dimerization or coupling with N.-. Homolysis of 2 produced always the more stable 3 apart from reactions of monomethylaziridines 1c,d where the primary radical i-3c,d is kinetically favoured. The amides R1CONHCHR4CHR2R3 (9, isopropylamides i-9c,d from 1c,d) were usually the main products. 9 arise from 3 either by H atom abstraction from THF (probably in sodium metal runs) or by reduction of 3 to carbanions 5 that abstract a proton from THF (N.- runs). Addition of 5a (R2-4 = H) to 1a gives finally the ketone 8a. Self reaction of primary radical 3a is dimerization. Self reaction of tertiary or secondary radicals is disproportionation when an allylamide arises. This isomerizes to an enamide unless it is conjugated. R2R3C=CHR4 and R1CONH2 arise (probably) always. The mechanism, possibly a cyclic process of anion 6, is not clear. Johann Ambrosius Barth 1996.
Ester Aminolysis: New Reaction Series for the Quantitative Measurement of Steric Effects
DeTar, DeLos F.,Delahunty, Claire
, p. 2734 - 2739 (2007/10/02)
Further development of theoretical methods for computing steric effects on chemical reactivity requires a large body of new reliable quantitative data for calibration and for testing.We report here on design criteria for reaction series suitable for obtaining these data and on a successful implementation that shows promise of providing access to a particularly broad range of steric hindrance and which additionally has shown a new form of steric hindrance.The series examined in the present study is ester aminolysis in the form RCOOC6H4NO2-p + R'NH2 in acetonitrile solution.A primary purpose of the examination has been to ascertain whether aminolysis may be a useful general series or whether known or unexpected complications might render it unsuitable.We have measured rate constants for a matrix of reactions using five different R groups and four different R' groups, each reaction at a series of concentrations of amine.This is the first systematic study of the sumultaneous action of steric hindrance effects in both the acylating agent and the entering nucleophile.The reactions showed both a second-order term k2 and a relatively less important third-order term k32.The Taft equation was applied to subsets of the rate constants.For each amine there were data for a set of esters for which the R group was the variable.The slopes ρs for these sets were nearly unity.For each ester there were corresponding data for a series of amine reactions in which R' was the variable.These sets also gave good correlations, but the slopes ρs' were considerably larger, about 2.3.This unusually large difference in response to structural effects in the acylating agent and in the nucleophile is unexpected and appears to arise from a new type of steric hindrance.An obvious explanation based on bond lengths proves to be quantitatively insufficient; that explanation postulates that there is greater hindrance for the amine because the C-N bond is short in comparison with the C-C bond.The difference may be due instead to a requirement for special orientation within the transition state, a matter currently under theoretical investigation.The k2 and the k3 sets gave similar correlations, an important finding in at least two respects.It means that steric effects are well-defined in this example of ester aminolysis, and it means also that the extra molecule of amine is far enough from the reaction center so that no additional steric hindrance results.The reactions observed in the present study cover a range of 5 powers of 10 in relative rate constants.Preliminary studies with other examples of aminolysis suggest that a range of relative rate constants covering well in excess of 12 powers of 10 should be observable.
